Plant growth regulant composition and method



United States Patent 3,334,991 PLANT GROWTH REGULANT COMPOSITION ANDMETHOD Howard A. Hageman, Southbury, and Winchester L. Hubbard,Woodbridge, Conn., assignors to Uniroyal, Inc., a corporation of NewJersey No Drawing. Original application Feb. 15, 1963, Ser. No. 258,923,now Patent No. 3,240,799, dated- Mar. 15, 1966. Divided and thisapplication Aug. 7, 1964, Ser.

No. 388,297 r 16 Claims. (Cl. 71--88) This application is a division ofour application Ser. No. 258,923, filed Feb. 15, 1963, now US. PatentNo. 3,240,799, which is a continuation-in-part of our application Ser.No. 89,654, filed Feb. 16, 1961, now abandoned.

This invention relates to plant growth regulants.

The plant growth regulants of the present invention are new compounds,namely N-disubstituted amino amic acids, in which the disubstitutedamino radical is selected from dialkylamino, l-pyrrolidyl, l-piperidyland 4-morpholinyl radicals, and the amic acid is selected from maleamic,alpha-alkylmaleamic, 'succinamic, alpha-alkyl succinamic,alpha-alkenylsuccinamic, alpha-arylsuccinamic, alpha-acyloxysuccinamic,alpha-alkylthiosuccinamic and alpha-arylthiosuccinamic acids, and thesalts, esters and imides of said N-disubstituted amino amic acids.

The N-disubstituted amino amic acids are prepared by reacting theselected 1,1-disubstituted hydrazine With the anhydride of the selecteddicarboxylic acid. The imides of these acids are prepared by removingwater from the acid by means of acetic anhydride.

Illustrative reactions for the formation of N-dimethylaminomaleamic acidand N-dimethylaminomaleimide are as follows:

The acids may be used as plant growth regulants in the form of the freeacids or their equivalent salts, such as the alkali salts, i.e. alkalimetal, ammonium or amine (substituted ammonium) salts, e.g. sodium,potassium, ammonium, methyl ammonium, dimethyl ammonium, trimethylammonium, ethyl ammonium, ethanol ammonium, diethanol ammonium, ortriethanol ammonium salts, since the salts give equivalent results. Thesalts may readily be formed directly from the acid and a selected basesuch as an alkali-metal hydroxide or carbonate, or ammonia, or an amine.

The esters of the N-disubstituted amino amic acids, such as the alkylesters having 1 to 12 carbon atoms in the esterifying radical and thealkenyl esters having 3 to 4 carbon atoms in the esterifying radical maybe used as plant growth regulants, e.g., the methyl, ethyl, propyl,butyl, octyl, dodecyl, allyl and methallyl esters. The

-esters may be formed by esterifying the selected N-disubstituted aminoamic acid with the selected alcohol,

3,334,991 Patented Aug. 8, 1967 "ice or by reacting the selected alcoholwith the imide of the selected N-disubstituted amino amic acid.

The N-disubstituted amino amic acids and the imides of the presentinvention may be represented by the general formulae OOH 0 H H o 0wherein R and R each stand for an alkyl group having 1 to 12 carbonatoms or R and R compositely stand for a (CH2)4, (CH2)5-' 01' group; andR and R each stand for hydrogen, or one of R and R stands for hydrogenand the other stands for a lower alkyl group having 1 to 8 carbon atoms,e.g. methyl, butyl, octyl; and R and R each stand for hydrogen, or oneof R and R stands for hydrogen and the other stands for one of thefollowing: an alkyl group having 1 to 12 carbon atoms, e.g. methyl,octyl, dodecyl; an alkenyl group having 3 to 12 carbon atoms, e.g.propenyl, tetra-propenyl (C H an aryl group, e.g. phenyl, tolyl,naphthyl; an acyloxy group, e.g. acetoxy; an alkylthio group having 1 to12 carbon atoms, e.g. methylthio, hexylthio, dodecylthio; an arylthioradical. e.g. phenylthio, tolylthio, naphthylthio.

After testing a variety of N-disubstituted amino amic acids and theirimides, it has been found that the essential structural arrangement forgrowth reg-ulant activity is one in which the carboxyl group of the acidis removed by two carbon atoms from the 0 B1 H H -CN-N moiety, and theintermediate two carbon moiety can not be part of an aromatic ring. Inthe chemicals of the present invention, the intermediate two carbonmoiety is part of a functionally aliphatic grouping.

Examples of chemicals of the present invention are:

Specific illustrative examples of the preparation of the compounds ofthe present invention are shown in Examples 1 to 10 below:

EXAMPLE 1 Preparation of N-dimethylaminomaleamic acid A three literthree necked flask containing a solution of 294 g. (3.0 moles) of maleicanhydride in 300 g. of acetonitrile was immersed in an ice bath. Over /2hour a solution of 180 g. (3.0 moles) of 1,1-dimethylhydrazine in 100 g.of acetonitrile was added from a dropping funnel as the reaction mixturewas stirred vigorously. During this addition the temperature of thereaction mixture did not exceed 30 C. Near the end of the addition alarge amount of a cream colored, crystalline solid precipitated from thesolution. After the addition was complete stirring was continued fortwenty minutes and then 700 ml. of ether was added to cause furtherprecipitation of the product from solution. Filtration of this reactionmixture gave a filter cake, which after washing with three 100 ml.portions of ether, amount to 428 g. (90% yield) ofN-dimethylaminomaleamic acid of M.P. 121-124 C.

A sample of this material after one recrystallization from acetone hadM.P. 123-125 C. Analysis.Calculated for C H N O 45.6% C, 6.3% H, 17.7%N. Found: 45.9% C, 6.5% H, 17.7% N.

EXAMPLE 2 Preparation of N-(4-morph0linyl)maleamic acid TheN-(4-morpholinyl)maleamic acid was obtained by reactingN-aminomorpholine with maleic anhydride by the procedure of Example 1.It is a colorless crystalline solid of M.P. 172174 C.Analysis.Calculated for O I-1 N 48.0% C, 6.0% H, 14.0% N. Found: 48.3%C, 6.1% H, 13.5% N.

The N-( l-pyrrOlidyDmaleamic acid and N-( l-piperidyl) maleamic acid maysimilarly be prepared from N-aminopyrrolidine and N-aminopipericline,respectively, and maleic anhydride.

EXAMPLE 3 Preparation of N-dimethylaminomaleimide To 312 g. (2.0 moles)of N-dimethylaminomaleamic acid of M.P. 121-124 C. (prepared as inExample 1) in a 1-liter Erlenmeyer flask was added 255 g. (2.5 moles) ofacetic anhydride. Over /2 hour this mixture was gradually warmed to 75C. on the steam bath. As the temperature reached 65-70 C., all of thesolid dissolved to give a clear amber solution. After keeping thissolution at 7580 C. for /2 hour, it was allowed to cool over about 1hour to 4550 C.

This solution was then subjected to vacuum distillation employing ashort (8-inch) still head. After the acetic acid and acetic anhydridehad been removed, the dark liquid residue was brought to a temperatureof 70 C. under a pressure of 23 mm. A yellow-orange liquid distillateamounting to 200 g. was then collected with a still head temperature inthe range of 68-84 C. and a pressure of 2-3 mm. As the distillatecooled, it set to a yelloworange crystalline mass. The residue in thedistilling flask consisted of 30-40 g. of a black brittle resin which isreadily soluble in water.

The distillate obtained above was then heated successively with several500 ml. portions of cyclohexane to 65-70 C. with agitation. Thisresulted in a two-phase system in which the cyclohexane layer became aclear gold yellow color. The lower layer consisted of a dark brownviscous oil. After agitation was stopped and the layers had separatedcleanly, the hot cyclohexane layer was decanted. After four more similarextractions, the combined cyclohexane solutions (ca. 2.5 liters) werecooled in an ice bath resulting in the precipitation of 133 g. (48%yield) of N-dimethylarninomaleimide as long bright yellow needles ofM.P. 8183 C. By recrystallizing a sample of this material again fromcyclohexane an analytical sample of M.P. 8283 C. was obtained having thefollowing elemental analysis. Calculated from C H N O 51.4% C, 5.7% H,20.0% N. Found: 51.7% c, 5.9% H, 19.5% N.

EXAMPLE 4 Preparation of N-dimethylaminosuccinamic acid To a solution of50 g. (.50 mole) of succinic anhydride in 150 g. of acetonitrile wasadded a solution of 30 g. (.50 mole) of 1,1-dimethylhydrazine in 50 g.of acetonitrile. After the exothermic reaction had subsided the mixturewas cooled in an ice bath and the precipitate collected by filtration. Ayield of 74 g. (92%) of N-dimethylaminosuccinamic acid as a colorlesscrystalline solid of M.P. 154l56 C. was obtained. A sample of thismaterial after recrystallization from ethanol gave colorless crystals ofM.P. 154l55 C.

EXAMPLE 5 Preparation of N-dimethylaminosuccinimide To 64 g. (.40 mole)of N-dimethylaminosuccinamic acid (prepared as in Example 4) was addedg. (.80 mole) of acetic anhydride. After heating this mixture to 100 C.for 15 to 20 minutes, there resulted a clear yellow solution. Afterkeeping at l00110 C. for 30 minutes, this solution was allowed to coolslowly (over 30- 40 minutes) to 5055 C. The acetic acid and aceticanhydride were then removed by distillation under a pressure of 5-10 mm.The residual liquid was then maintained at 80-85 C. for 15 minutes undera pressure of 3-4 mm. There was obtained 53 g. of a clear light amberliquid which set to a crystalline mass after cooling in an ice bath. Byrecrystallizing this material from ether there was obtained 32 g. ofN-dimethylaminosuccinimide as colorless needles of M.P. 5 355 C.

EXAMPLE 6 Preparation of ethyl N-dimethylaminosuccinamate This exampleillustrates the preparation of an ester from an N-disubstituted aminoamic acid.

Into a mixture of 40 g. (.25 mole) of N-dimethylaminosuccinamic acid and300 ml. of absolute ethanol was passed 10 g. of anhydrous HCl. Afterrefluxing this mixture for 2 hours all the solid dissolved to give aclear solution. Over an additional 1 hour, one-half of the ethanol wasremoved by distillation. After cooling this solution in an ice bath for1 hour and then adding ml. of ether, the precipitated solid wascollected by filtration and Washed with ether. There was obtained 38 g.of the hydrochloride of ethyl N-dimethylaminosuccinamate as colorlesscrystals of M.P. 129 C.

A sample of 11.2 g. (.05 mole) of this ester hydrochloride was coveredwith 200 ml. of ether. After adding 5.0 g. .05 mole) of triethylamineand vigorously agitating for /2 hour, the mixture was filtered and thefilter cake washed with two 50 m1. portions of ether. The filtrate wasthen reduced to a volume of ml. by distillation. Upon cooling this ethersolution in an ice bath and subsequently collecting the precipitatedsolid by filtration, there was obtained 6.2 g. of ethylN-dimethylaminosuccinamate as colorless crystals of M.P. 70-72" C.

EXAMPLE 7 Preparation 0] n-butyl N-dimethylaminosuccinamate This exampleillustrates the preparation of an ester from an imide of anN-disubstituted amino amic acid.

A solution of 14.2 g. (.10 mole) of N-dimethylaminosuccinimide in 74 g.of n-butanol was treated with anhydrous HCl until 3.6 g. (.10 mole) hadbeen absorbed. This slurry was then heated to 105-115 C. for 2 hoursgiving a clear, colorless solution. After cooling in an ice bath, awhite, crystalline solid precipitated. After adding 50 ml. of ether,filtration gave 19.5 g. of colorless crystals of M.P. 102104 C. Thiscompound is the hydrochloride of n-butyl N-dimethylaminosuccinamate.

A sample of 12.6 g. (.05 mole) of this hydrochloride was covered with150 ml. of ether. After adding 5.0 g. (.05 mole) of triethylamine, themixture was vigorously agitated for /2 hour. The solid triethylaminehydrochloride was then removed by filtration and the ether filtratecooled in an ice bath. Filtration of the precipitated solid gave 4.5 g.of n-butyl N-dimethylaminosuccinamate as colorless crystals of M.P. 4547C.

EXAMPLE 8 Preparation of N-dimethylamino-alpha-tetrapropenylsuccinam'icacid The tetrapropenylsuecinic anhydride employed was obtained fromMonsanto Chemical Company and is designated to contain a C H group inthe alpha position. By reacting this anhydride with an equimolar amountto 1,'1-dimethylhydrazine in acetonitrile as the reaction medium a clearyellow solution is obtained. After removing the acetonitrile from thissolution by distillation under vacuum the N dimethylamino alphatetrapropenylsuccinamic acid is obtained as a-clear yellow viscousliquid.

EXAMPLE 9' Preparation of N-dim ethylamino-alphaacetoxysuccinam'ic acidTo a solution of 15 g. (.10 mole) of alpha-acetoxysuccinic anhydride, ofM.P. 5657 C., in 20 g. of acetonitrile, there was added, in smallportions 6.0 g. (.10 mole) of 1,1-dimethylhydrazine. During the mixingan ice bath was employed to prevent the temperature of the reactionmixture from exceeding 35 C. After allowing this mixture to' stand forone hour, the .acetonitrile was removed by distillation under vacuum. Bykeeping the residue at a temperature of 40-45 C. for two hours under apressure of 2-3 mm., there was obtained 21 g. of a viscous light brownliquid which partially crystallized after standing several hours.

EXAMPLE 10 Preparation of N-dimethylamino-alphaphenylthiosuccinimide Toa solution of 14 g. .10 mole) of N-dimethylaminomaleimide (prepared asin Example 3) in 20 g. of henzene was added 11 g. (.10 mole) ofthiophenol (phenyl mercaptan). After warming this mixture to 6065 C., afew crystals of benzoyl peroxide were added and the mixture was allowedto stand for 1 /2 hours. After removing the benzene by distillation, theresidue was kept at 65-70 C. under a pressure of 2-3 mm. for /2 hour.The residual yellow liquid (24 g.) was dissolved in 70 ml. of warmethanol. After cooling this solution in an ice bath, the precipitatedsolid was collected by filtration. There was obtained 17 g. ofN-dimethylamino-alpha-phenylthiosuccinimide as colorless crystals, M.P.70--7l C.

The sodium salt of N-dimethylamino-alpha-phenylthiosuccinamic acid maybe prepared from the N-dimethylamin-alpha-phenylthiosuccinimide byreaction with sodium hydroxide, and the free acid may be obtained fromthe sodium salt by treatment with a strong inorganic acid, e.g.hydrochloric acid.

N dimethylamino alpha alkylthiosuccinimides may be prepared similarly tothe N dimethylamino alphaphenylthiosuccinimide by reacting the Ndimethylaminomaleimide with the selected alkyl mercaptan.

The chemicals of the present invention may be applied to plants, whichterm includes various plant parts such as seeds, flowers, fruits,vegetables, roots and foliage in various manners. Seeds may be treateddirectly with the chemical before planting, or seeds may be treated withthe chemical by incorporating the chemical in the soil before or afterplanting the seeds. The chemicals may be applied to plants in an inertmedium as a dust in admixture with a powdered solid carrier, such as thevarious mineral silicates, e.g. mica, talc, pyrophyllite and clays or asan aqueous composition. The chemicals may be applied in admixture withsmall amounts of surface-active wetting agents, which may be anionic,non-ionic, or cationic surface active agents, generally as aqueouscompositions. The chemicals may be dissolved in organic solvents such asacetone, benzene, or kerosene, and the solutions of the chemicalsemulsified in water with the aid of surfaceactive agents. Suchsurface-active agents are well known and reference is made to US. PatentNo. 2,547,724, columns 3 and 4, for detailed examples of the same. Thechemicals of the invention may be admixedv with powdered solid carriers,such as mineral silicates, together with a surface-active agent so thata wettable powder may be obtained which may be applied directly toplants, or which may be shaken up with water for application to theplants in that form.

The effectiveness of the chemicals of the present invention asnon-injurious plant growth regulants, and particularly as dwarfingagents, is illustrated in the following examples:

EXAMPLE A This example illustrates the treatment of growing plants withthe chemicals of the present invention.

Water solutions or dispersions of the chemicals were prepared containing5000 parts per million (p.p.m.) of various chemicals of the inventionand a small amount of a surface-active wetting agent (polyoxyethylenesorbitan monolaurate) which is known to be inactive in the tests run. 1

Peanut plants in the 2 to 3 leaf stage were sprayed to run off withaqueous compositions prepared as above containing 5000 p.p.m. ofN-dimethylaminomaleamic acid, N-di-n-octylaminomaleamic acid,N-dimethylaminocitraconamic acid, N-dimethylaminomaleimide,N-(4-morpholinyl)maleamic acid, N-(4-morpholinyl)maleimide,N-dimethylaminosuccinamic acid, N-dimethylaminosuccinimide, methylN-dimethylaminosuccinamate, ethyl N dimethylamiuosuccinamate, isopropylN dimethylaminosuccinamate, and n-butyl N-dimethylaminosuccinamate, Ndimethylamino-alpha-tetrapropenylsuccinamic acid,N-dimethylamino-alpha-phenylsuccinamic acid, and N dimethylamino alphaphenylthiosuccinimide. The treated plants and untreated control plantswere then placed in a chamber having humidity and a temperature of 75 F.After 24 hours, they were taken out and placed in a greenhouse. Theplants were examined two to four weeks after the application of thechemicals. There was a decided dwarfing or shortening of the internodesof the peanut plants treated with the chemicals on comparison with theuntreated control plants.

Similar tests to the above on pinto bean plants with application ofsolutions of 2500, 1250 and 625 ppm. of the sodium, ammonium,monoethylamine, diethylamine, triethylamine and diethanolamine salts ofN-dimethylamino-succinamic acid (which salts were prepared by adding therespective bases to 10% solutions of the free acid to give pH of 6.5)showed a decided dwarfing of the plants treated with the chemicals oncomparison with the untreated control plants.

, Other crops such as soybeans, and squash show similar dwarfing ontreatment with the chemicals of the present invention.

EXAMPLE B This example illustrates the direct treatment of seeds withthe chemicals of the present invention.

Pinto beans seeds were immersed in 100 ml. of aqueous compositionscontaining 1000 parts per million of the following chemicals preparedsimilarly to the compositions in Example A: N-dimethylaminomaleamicacid, N- di n dodecylaminomaleamic acid, N dimethylaminomaleimide,N-(4-morpholinyl maleamic acid, N-tdimethylaminosuccinamic acid, ethyl Ndimethylaminosuccinamate, N-dirnethylamino alpha tetrapropenylsuccinamicacid, N-dimethyamino-alpha-acetoxysuccinamic acid,N-dimethylaminosuccinimide, N-dimethylaminoalpha-phenylthiosuccinimide.After four hours, the seeds were removed, washed thoroughly in water forseveral minutes, and planted in soil contained in four-inch pots.Untreated control seeds were similarly planted. Observations two to fourweeks after planting showed decided dwarfing of the plants treated withthe chemicals on comparison with the untreated control plants.

EXAMPLE C This example illustrates seed treatment with the chemical byincorporating the chemicals in the soil.

Two-tenths of a gram of each of the following dry chemicals were mixeduniformly with lb. of dry sand: N-dimethylaminomaleamic acid,N-dimethylaminomaleamide, N-dimethylaminosuccinamic acid,N-dimethylaminosuccinimide, andN-dirnethylaminoalpha-phenylthiosuccinimide. The sand and chemicalmixtures were then each added to four and a quarter pounds of a 4:1 soiland sand mixture, and were tumbled for five minutes. At the end of thistime, the chemicals were uniformly distributed throughout the soil andsand mixture at a rate of one hundred parts of the chemicals per millionparts of the soil and sand. The thus treated soil and sand were thenplaced in 4-inch pots in which pinto bean seeds were planted. Pinto beanseeds were also planted in pots contaiing untreated control soil andsand. Observations after two to four weeks showed definite dwarfing ofthe plants from seeds that were planted in soil treated with thechemicals of the present invention in comparison with the plants fromseeds that were planted in the untreated control soil.

Having thus described our invention, what we claim and desire to protectby Letters Patent is:

1. A plant growth regulant composition which comprises a plant growthregulating, but non-injurious, amount of an N-disubstituted amino amicacid, in which:

(I) the disubstituted amino radical is selected from the groupconsisting of dialkylamino in which each alkyl group has 1 to 12 carbonatoms, l-pyrrolidyl, l-piperidyl, 4-morpholinyl, and

(II) the amic acid is one having the formula:

HOOCCR =CR CONH wherein either R or R is hydrogen and the other is:hydrogen or an alkyl group having 1 to 8 carbon atoms, or HOOCCHR CHRCONH wherein R or R is hydrogen and the other is:

hydrogen, an alkyl having 1 to 12 carbon atoms,

an alkenyl having 3 to 12 carbon atoms, a phenyl, a tolyl, a naphthyl,an acetoxy, an alkylthio having 1 to 12 carbon atoms, phenylthio,tolylthio, or naphthylthio group; or the alkali metal salts, theammonium salts, the amine salts, the alkyl esters in which the alkylgroup has 1 to 12 carbon atoms, the allyl esters, the rnethallyl esters,or the imides of said N-disubstituted amino amic acid; and a surfaceactive agent.

2. The plant growth regulant of claim 1 wherein the amic acid ismaleamic acid.

3. The plant growth regulant of claim 1 wherein the amic acid issuccinamic acid.

4. A method of regulating plant growth which comprises treating plantswith a plant growth regulating, but non-injurious, amount of anN-disubstituted amino amic acid, in which:

(I) the disubstituted amino radical is selected from the groupconsisting of dialkylamino in which each alkyl group has 1 to 12 carbonatoms, l-pyrrolidyl, 1- piperidyl, 4-morpholinyl, and

(II) the amic acid is one having the formula:

HOOCCR =CR CONH wherein either R or R is hydrogen and the other is:hydrogen or an alkyl group having 1 to 8 carbon atoms, or HOOCCHR -CHRCONH wherein R or R is hydrogen and the other is:

hydrogen, an alkyl having 1 to 12 carbon atoms,

an alkenyl having 3 to 12 carbon atoms, a phenyl, a tolyl, a naphthyl,an acetoxy, an alkylthio having 1 to 12 carbon atoms, phenylthio,tolylthio, or naphthylthio group; or the alkali metal salts, theammonium salts, the amine salts, the alkyl esters in which the alkylgroup has 1 to 12 carbon atoms, the allyl esters, methallyl esters, orthe imides of said N-disubstituted amino amic acid.

5. The method of claim 4 wherein said amic acid is maleamic acid.

6. The method of claim 4 wherein said amic acid is succinamic acid.

7. A method of regulating plant growth which comprises treating seedswith a plant growth regulating, but non-injurious, amount of anN-disubstituted amino amic acid, in which:

(I) the disubstituted amino radical is selected from the groupconsisting of dialkylamino in which each alkyl group has 1 to 12 carbonatoms, l-pyrrolidyl, 1- piperidyl, 4-morpholinyl, and

(II) the amic acid is one having the formula:

HOOCCR CR CONH wherein either R or R is hydrogen and the other is:hydrogen or an alkyl group having 1 to 8 carbon atoms, or HOOCCHR CHRCONH wherein R or R is hydrogen and the other is:

hydrogen, an alkyl having 1 to 12 carbon atoms,

an alkenyl having 3 to 12 carbon atoms, a phenyl, a tolyl, a naphthyl,an acetoxy, an alkylthio having 1 to 12 carbon atoms, phenylthio,tolylthio, or naphthylthio group; or the alkali metal salts, theammonium salts, the amine salts, the alkyl esters in which the alkylgroup has 1 to 12 carbon atoms, the allyl esters, the methallyl esters,or the imides of said N-disubstituted amino amic acid.

8. The method of regulating plant growth of claim 7 wherein the amicacid is maleamic acid.

9. The method of regulating plant growth of claim 7 wherein the amicacid is succinamic acid.

10. A method of regulating plant growth which comprises treating a plantwith a plant growth regulating, but non-injurious, amount of anN-dialkylaminomaleamic acid in which each alkyl group has 1 to 12carbons.

11. A method of regulating plant growth which comprises treating a plantwith a plant growth regulating, but non-injurious, amount of anN-dialkylaminomaleamic acid.

12. A method of regulating plant growth which comprises treating a plantwith a plant growth regulating, but non-injurious, amount of anN-dialkylarninosuccinamic acid in which each alkyl group has 1 to 12carbons.

13. A method of regulating plant growth which comprises treating a plantwith a plant growth regulating, but non-injurious, amount of anN-dimethylaminosuccinarnic acid.

14. A method of regulating plant growth which comprises treating a plantwith a plant growth regulating, but non-injurious, amount of adimethylaminomaleimide.

15. A method of regulating plant growth which comprises treating a plantwith a plant growth regulating, but non-injurious, amount of adimethylaminosuccinimide.

16. A method of regulating plant growth which comprises treating a plantwith a plant growth regulating, but non-injurious, amount of abutyl-N-dimethylaminosuccinamate.

(References on following page) 9 10 References Cited OTHER REFERENCESUNITED STATES PATENTS Steck: J. Am. Chem. Soc., vol. 76, pp. 44547(1954).

Price X Primary Examiner- FOREIGN PATENTS 5 JAMES o. THOMAS, Examiner.

176,563 11/1953 Austria.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,334,991 August 8 1967 Howard A. Hageman et al.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as show below:

Column 7 lines 54 and 55 Column 8 l Ines 9 and lines 3? and 40, before"plienylthio": "tolylti i nd naphthylthlo", each occurrence, insert aColumn 8 line 13 before "methallyl" insert the Signed and sealed this12th day of August 1969.

(SEAL) Attest:

Edward M. Fletcher, Jr. WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Attesting Officer

1. A PLANT GROWTH REGULANT COMPOSITION WHICH COMPRISES A PLANT GROWTHREGULATING, BUT NON-INJURIOUS, AMOUNT OF AN N-DISUBSTITUTED AMINO AMICACID, IN WHICH: (I) THE DISUBSTITUTED AMINO RADICAL IS SELECTED FROM THEGROUP CONSISTING OF DIALKYLAMINO IN WHICH EACH ALKYL GROUP HAS 1 TO 12CARBONS ATOMS, 1-PYRROLIDYL, 1-PIPERIDYL, 4-MORPHOLINYL, AND (II) THEAMIC ACID IS ONE HAVING THE FORMULA:
 2. THE PLANT GROWTH REGULANT OFCLAIM 1 WHEREIN THE AMIC ACID IS MALEAMIC ACID.